Crystalline metalloaluminum borates

ABSTRACT

The preparation, structure, and properties of solid inorganic materials containing aluminum, boron, oxygen and at least one Group VIII metallo element, selected from the group consisting of cobalt and nickel is described. Also described is the use of such materials in catalytic compositions for the conversion of organic compounds. In particular, the new materials having the general formula: 
     
         (x)(M.sub.m :M&#39;.sub.n)O.(y)Al.sub.2 O.sub.3.(z)B.sub.2 O.sub.3 
    
     where M and M&#39; are metallo elements selected from the group consisting of nickel and cobalt, m and n are numbers form 0 to 1, inclusive, such that m+n=1, and x, y and z are numbers representing molar amounts of the oxides are described as well as the use of such materials in various catalyzed processes including hydrogenation of hydrocarbons and oxygen containing hydrocarbons, dehydrogenation to functionalize alkylaromatic compounds, isomerization of alkylaromatic compounds, oligomerization of olefins, and oxidation of hydrocarbons and oxygen containing hydrocarbons.

This is a division of application Ser. No. 07/669,903, filed Mar. 15,1991 now U.S. Pat. No. 5,084,259 which is a continuation of applicationSer. No. 233,266 filed Aug. 17, 1988 now abandoned.

BACKGROUND OF THE INVENTION

The present invention relates to crystalline inorganic materialscontaining at least one Group VIII metallo element selected from thegroup consisting of cobalt and nickel, aluminum, boron and oxygen havingspecified X-ray patterns. This invention also relates to solid inorganicmaterials containing at least one Group VIII metallo element, aluminum,boron and oxygen made by calcining a mixture comprising sources ofdivalent metallo ions, alumina and boria at elevated temperature, andthe use of such solid in catalytic compositions for the conversion oforganic compounds, particularly hydrogenation of hydrocarbons and oxygencontaining hydrocarbons, dehydrogenation to functionalize alkylaromaticcompounds, isomerization of alkylaromatic compounds, oligomerization ofolefins, and oxidation of hydrocarbons and oxygen containinghydrocarbons.

The use of an active metallo element or a supported metallo elementcomposition containing aluminum and boron as a conversion catalyst isknown in the art. U.S. Pat. No. 3,883,442 to McArthur is illustrative ofprior art disclosing the superiority of a supported active metalcatalyst to resist shrinkage at high temperatures (up to 1600° C.) bystabilization of a preformed alumina catalyst support. McArthur statesstabilization was achieved by impregnating an alumina support with asolution of a boron compound which is thermally decomposable to B₂ O₃,followed by drying and calcining of the impregnated support attemperatures below about 1500° C., but sufficiently high to decomposethe boron compound. McArthur also discloses that the most commonly usedtechnique of preparing a supported metallo element catalyst involved:following calcination, impregnating in conventional manner the aluminasupport material containing some retained B₂ O₃ with a solution of thedesired metal salt, preferably those that are thermally decomposable togive the corresponding metal oxides and/or sulfides, and calcining thesalt-impregnated support to convert the impregnated salt to the activecatalytic form. McArthur neither discloses nor suggests a mixed oxidecomposition of a metallo element, aluminum, and boron.

In U.S. Pat. No. 3,954,670 to Pine a boria-alumina based catalyst isdisclosed in the combination of a metallo element and a boria-aluminacatalyst support materials prepared by hydrolysis of a mixture ofaluminum alkoxide and boron alkoxide in the presence of water at atemperature in the range of 20° to 100° C. The disclosed catalystcompositions, said to be useful for desulfurization, denitrogenation,reforming and other hydrocarbon conversion processes, included bothcobalt and nickel as metallo elements in combinations with theboria-alumina catalyst composition disclosed in Pine and, optionally, acrystalline aluminosilicate zeolite with or without rare earth elements.However, Pine neither discloses nor suggests any crystalline mixed oxidecomposition of a metallo element, aluminum, and boron.

Zletz in U.S. Pat. No. 4,729,979, which is hereby incorporated byreference, discusses the characteristics of a good catalyst and/orcatalyst support and a new crystalline copper aluminum boratecharacterized by a specific X-ray diffraction pattern, surface area andpore volume which is at least partially reducible with hydrogen at atemperature no more than 350° C. to a composition containing zero valentcopper and Al₄ B₂ O₉. Satek in U.S. Pat. No. 4,590,324, which is herebyincorporated by reference, discusses using the new crystalline copperaluminum borate as a catalyst to dehydrogenate alkylaromatics toalkenylaromatics. Zletz et al. in U.S. Pat. No. 4,645,753, which ishereby incorporated by reference, discusses doping the new crystallinecopper aluminum borate to contain an alkali metal or alkaline earthmetal element for use as a catalyst to dehydrogenate alkylaromatics toalkenylaromatics. The Zletz, Satek, and Zletz et al. patents alone or incombination neither disclose nor suggest a mixed oxide composition ofaluminum, boron, and a metallo element without copper. Furthermore,these patents disclose crystalline copper aluminum borate havingsignificant X-ray diffraction lines which are substantially differentfrom X-ray diffraction patterns for crystalline materials of the presentinvention.

Schwab and Bertaut disclose the preparation of a single crystal of aboroaluminate of nickel in Bull. Soc. Fr. Mineral. Cristollogr. (1970),93, 255-257, "Structure di boroaluminate B₂ O₃.Al₂ O₃.4NiO" which ishereby incorporated by reference, by mixing the oxides B₂ O₃, Al₂ O₃ andNiO in the mol ratio of 1:1:4 plus a large excess of B₂ O₃ [sic],heating the mixture to 1300° C., cooling the hot mixture carefully toroom temperature at a rate of 50° C. per hour, and treating the cooledproduct with dilute nitric acid to dissolve excess borax providingsingle crystals about 2-3 mm long. The atomic coordinates for a singlecrystal structure are reported, however no powder x-ray diffractionpattern is reported. Boroaluminates of nickel produced by the indicatedroute are believed to be well-defined, dense crystalline particles whichhave an extremely low surface area due to heating a mixture of oxides toa temperature of 1300° C.

The general object of the present invention is to provide a newcomposition useful as a catalyst to convert organic compounds to othercompounds.

Another general object of this invention is to produce a new catalystwhich is useful to hydrogenate hydrocarbons and oxygen containinghydrocarbons, dehydrogenate alkylaromatic compounds, isomerizealkylaromatic compounds, oligomerize olefins, and oxidize hydrocarbons,particularly aromatic hydrocarbons.

Other objects and advantages of the invention will become apparent uponreading the following detailed description and appended claims.

SUMMARY OF THE INVENTION

In one aspect, the present invention is a crystalline inorganic materialcomprising aluminum, boron, oxygen and at least one Group VIII metalloelement, preferably selected from the group consisting of cobalt andnickel having an X-ray diffraction pattern comprising significant linessubstantially as shown in at least one of the tables set out herein asTable I, Table II, Table III and Table IV.

In another aspect, the invention describes the preparation andproperties of a crystalline inorganic material comprising aluminum,boron, oxygen and at least one Group VIII metallo element, preferablyselected from the group consisting of cobalt and nickel made bycalcining a mixture containing sources of divalent nickel ions and/ordivalent cobalt ions, alumina and boria at elevated temperature, thesolid providing an X-ray pattern comprising lines substantially as shownin at least one of the tables set out herein as Table I, Table II, TableIII and Table IV.

In a preferred embodiment the present invention is a crystallineinorganic material comprising aluminum, boron, oxygen and nickel havingan X-ray diffraction pattern comprising significant lines substantiallyas shown in Table I.

                  TABLE I                                                         ______________________________________                                        Principal XRD Lines                                                                  Interplanar                                                                   Spacing.sup.1                                                                         Assigned                                                              d, A°                                                                          Strength.sup.2                                                 ______________________________________                                               6.41 ± 0.2                                                                         W                                                                     4.09 ± 0.10                                                                        M                                                                     2.90 ± 0.08                                                                        M                                                                     2.53 ± 0.05                                                                        M                                                                     2.50 ± 0.05                                                                        VS                                                                    1.92 ± 0.05                                                                        W                                                                     1.74 ± 0.04                                                                        W                                                                     1.55 ± 0.04                                                                        W                                                                     1.50 ± 0.04                                                                        W                                                                     1.46 ± 0.03                                                                        W                                                              ______________________________________                                         .sup.1 Angstroms                                                              .sup.2 VW = very weak; W = weak; M = medium; S = strong; VS = very strong

As is generally known, the assigned strengths in X-ray diffractionpatterns may vary depending upon the characteristics of the sample. Theobserved line strength in any particular sample may vary from anothersample. Also, X-ray diffraction lines of a particular crystallinematerial may be obscured by lines from other materials present in ameasured sample.

In another aspect, the invention describes the preparation andproperties of a solid inorganic material containing nickel, aluminum,boron and oxygen having the empirical formula NiAlBO₄ and providing anX-ray pattern comprising the X-ray diffraction lines and assignedstrengths shown in Table I.

Another preferred embodiment of the present invention is a crystallineinorganic material prepared as described above to form a solidcomposition containing nickel, aluminum, boron and oxygen having anX-ray diffraction pattern comprising lines substantially as shown inTable II.

                  TABLE II                                                        ______________________________________                                        Principal XRD Lines                                                                  Interplanar                                                                   Spacing.sup.1                                                                         Assigned                                                              d, A°                                                                          Strength.sup.2                                                 ______________________________________                                               5.01 ± 0.2                                                                         M                                                                     4.55 ± 0.15                                                                        M                                                                     3.66 ± 0.08                                                                        W                                                                     2.51 ± 0.05                                                                        S                                                                     2.47 ± 0.05                                                                        VS                                                                    2.29 ± 0.05                                                                        M                                                                     2.12 ± 0.05                                                                        W                                                                     2.08 ± 0.05                                                                        W                                                                     1.99 ± 0.05                                                                        M                                                                     1.87 ± 0.05                                                                        M                                                                     1.54 ± 0.04                                                                        W                                                                     1.47 ± 0.04                                                                        W                                                                     1.46 ± 0.03                                                                        M                                                                     1.44 ± 0.03                                                                        W                                                              ______________________________________                                         .sup.1 Angstroms                                                              .sup.2 VW = very weak; W = weak; M = medium; S = strong; VS = very strong

In another aspect, the invention describes the preparation andproperties of a solid inorganic material containing nickel, aluminum,boron and oxygen having the empirical formula Ni₂ AlBO₅ and providing anX-ray pattern comprising the X-ray diffraction lines and assignedstrengths shown in Table II.

In another preferred embodiment of the present invention is acrystalline inorganic material containing cobalt, aluminum, boron andoxygen having an X-ray diffraction pattern comprising linessubstantially as shown in Table III.

                  TABLE III                                                       ______________________________________                                        Principal XRD Lines                                                                  Interplanar                                                                   Spacing.sup.1                                                                         Assigned                                                              d, A°                                                                          Strength.sup.2                                                 ______________________________________                                               5.03 ± 0.2                                                                         M                                                                     4.60 ± 0.15                                                                        M                                                                     3.68 ± 0.10                                                                        W                                                                     2.52 ± 0.06                                                                        VS                                                                    2.32 ± 0.05                                                                        W                                                                     2.30 ± 0.05                                                                        W                                                                     2.12 ± 0.05                                                                        W                                                                     2.02 ± 0.04                                                                        W                                                                     1.89 ± 0.05                                                                        M                                                                     1.56 ± 0.04                                                                        W                                                                     1.50 ± 0.04                                                                        W                                                                     1.47 ± 0.03                                                                        W                                                                     1.37 ± 0.02                                                                        W                                                              ______________________________________                                         .sup.1 Angstroms                                                              .sup.2 VW = very weak; W = weak; M = medium; S = strong; VS = very strong

In another aspect, the invention describes the preparation andproperties of a solid inorganic material containing cobalt, aluminum,boron and oxygen having the empirical formula Co₂ AlBO₅ and providing anX-ray pattern comprising the X-ray diffraction lines and assignedstrengths shown in Table III.

Another preferred embodiment of the present invention is a crystallineinorganic material prepared as described above to form a solidcomposition containing cobalt, nickel, aluminum, boron and oxygen havingan X-ray diffraction pattern comprising lines substantially as shown inTable IV.

                  TABLE IV                                                        ______________________________________                                        Principal XRD Lines                                                                  Interplanar                                                                   Spacing.sup.1                                                                         Assigned                                                              d, A°                                                                          Strength.sup.2                                                 ______________________________________                                               5.02 ± 0.2                                                                         M                                                                     4.57 ± 0.15                                                                        M                                                                     3.66 ± 0.10                                                                        W                                                                     2.51 ± 0.05                                                                        S-VS                                                                  2.48 ± 0.05                                                                        S-VS                                                                  2.30 ± 0.05                                                                        M                                                                     2.00 ± 0.05                                                                        M-W                                                                   1.88 ± 0.05                                                                        M-W                                                            ______________________________________                                         .sup.1 Angstroms                                                              .sup.2 VW = very weak; W = weak; M-W = medium to weak; M = medium; S =        strong; S-VS = strong to very strong; VS = very strong                   

Another aspect of the invention describes the preparation and propertiesof a solid material having the empirical formula

    4(Co.sub.m :Ni.sub.n)O.Al.sub.2 O.sub.3.B.sub.2 O.sub.3

where m and n are numbers from 0.0 to 1.0 such that m+n=1 and providingan X-ray pattern comprising the X-ray diffraction lines and assignedstrengths shown in Table IV.

In still another aspect, the invention describes the use of such solidmaterials in catalytic compositions for the conversion of organiccompounds. In a further aspect, the invention describes the use of suchmaterials for hydrogenation of hydrocarbons and oxygen containinghydrocarbons, for example in the conversion of aromatic esters to thecorresponding aldehydes. In a further aspect, the invention describesthe use of such materials for dehydrogenation of alkylaromaticcompounds. In a further aspect, the invention describes the use of suchmaterials for isomerization of alkylaromatic compounds. In a furtheraspect, the invention describes the use of such materials foroligomerization of olefins, and in still a further aspect, the inventiondescribes the use of such materials for oxidizing and/or partiallyoxidizing one or more oxidizable substituents on an aromatic compoundwith the aromatic compound in a fluid-phase to form a partially oxidizedaromatic product and/or a carboxylic acid derivative.

DETAILED DESCRIPTION OF THE INVENTION

The nickel and/or cobalt, aluminum, boron, and oxygen solid materials ofthe present invention can be prepared by calcining a mixture of a sourceof nickel(II) and/or cobalt(II) ions, a source of alumina, and a sourceof boria.

Conditions of calcination include a temperature within the range ofabout 600° C. to about 1500° C., a pressure of at least about oneatmosphere, and a reaction time that is sufficient to affect formationof a crystalline metalloaluminum borate. Increasing pressure andtemperature of calcination, generally affect formation of a crystallinemetalloaluminum borate in a shorter reaction time. However, a hightemperature of calcination typically results in crystalline materialswith less desirably surface properties, for example low surface area.Preferred calcination temperatures are in a range of about 700° C. to1100° C. Calcination can be carried out in air, nitrogen or other inertgases. A preferred atmosphere for calcination contains oxygen.

The solid materials of this invention can be prepared generally bydispersing the required ingredients in a liquid medium, preferably anaqueous medium, removing substantially all the liquid to formsuperficially dry mixture, and calcining the dry mixture.

When a liquid medium is used, the source of nickel(II) or cobalt(II)ions can be any reasonably soluble salt of nickel(II), cobalt(II), orprecursor thereof which is at least partially soluble in the dispersingliquid, such as the acetate, formate, carbonate, chloride, bromide,sulfate and the like. Nickel(II) and cobalt(II) salts containing adecomposable anion such as nickel nitrate, nickel acetate, nickelformate, nickel carbonate, cobalt nitrate, cobalt acetate, cobaltformate, cobalt carbonate, etc. are preferred.

Typically, best results are obtained when each of the sources used ischosen to reduce the content of foreign anions and cations in thereaction mix.

The source of alumina is any material capable of producing alumina, butpreferred is a well dispersed, liquid source such as an alumina sol.

The source of boria is a material such as borate or boric acid with pureboric acid being preferred.

Typically, the mole ratios of the various reactants can be varied toproduce the solid of this invention. Specifically, the mole ratios interms of oxides of the initial reactant concentrations are characterizedby the general mixed oxide formula

    (x)(M.sub.m :M'.sub.n)O.(y)Al.sub.2 O.sub.3.(z)B.sub.2 O.sub.3

where M and M' are metallo elements selected from the group consistingof nickel and cobalt, m and n are numbers from 0.0 to 1.0, inclusive,such that m+n=1, and x, y and z are numbers representing molar amountsof the oxides of the source reagents. A preferred ratio of m/n is in arange of about 0.01 to about 0.5. A preferred ratio of n/m is in a rangeof about 0.01 to about 0.5. The mole ratios of (M_(m) :M'_(n))O/B₂ O₃,calculated as x/z are about 0.1 to about 100, preferably about 0.15 toabout 40, and most preferably about 0.2 to about 20, and the mole ratiosof Al₂ O₃ /B₂ O₃, calculated as y/z can range up to about 20, preferablyabout 0.01 to about 10 and more preferably about 0.02 to about 5.

In somewhat greater detail, a preferred procedure is to dissolve theboria source and disperse the alumina r source in water with mixing in ablender for about 3-5 minutes, then adding an aqueous solution of asource of a Group VIII metallo element to the blender followed bygelation with ammonia.

Typically, the pH of the aqueous mixture is less than about 11. If thereaction media is too acid or too basic, the desired solid generallywill not form or other contaminating phases are formed in addition tothe desired product. To some extent the pH of the reaction mixturecontrols surface properties of the final calcined solid material.Preferably, the pH of the reaction mixture is in a range from about 3 toabout 10, more preferably about 4 to about 9, in order to gel thereaction mixture. If desired, the pH can be adjusted with a base such asammonia, ethylenediamine, tetramethylammonium hydroxide and the like.Preferred is the use of ammonium hydroxide. The presence of the ammoniaas well as other volatile components in the gelled mixture, such asacetate ion, nitrate ion, etc., is advantageous in providing the finalcalcined solid with sufficiently high surface area and porositydesirable for catalytic reactions.

The gelled mixture is allowed to air dry, usually for about 1-3 days,followed by vacuum drying, typically at a pressure of about 0.3atmosphere for about 15 to 25 hours at about 100° C. to 150° C. with anitrogen purge.

The superficially dry mixture is calcined, preferably at a temperaturewithin the range of about 700° to about 1100° C. for a reaction timethat is sufficient to affect formation of a crystalline metalloaluminumborate, typically a reaction time within the range of about 2 to about30 hr. Samples of material can be removed during calcination to checkthe degree of crystallization and determine the optimum calcinationtime.

The crystalline material formed can be crushed to a powder or to smallparticles and extruded, pelletized, or made into other forms suitablefor its intended use. In a preferred embodiment of the above-describedmethod, the crystalline material formed can be washed with a solvent,preferably an aqueous solvent, which removes impurities such as excessboria, without destroying the crystalline material formed, mildly driedfor anywhere from a few hours to a few days at varying temperatures,typically about 50° to about 225620 C., to form a dry cake which canthen be treated as required for its intended use.

The solid materials made by this invention can be admixed with orincorporated within various binders or matrix materials depending uponthe intended process use. They are combined with active or inactivematerials, synthetic or naturally occurring oxides, as well as inorganicor organic materials which would be useful for binding such substances.Well-known materials include silica, silica-alumina, alumina, magnesia,titania, zirconia, alumina sols, hydrated aluminas, clays such asbentonite or kaolin, Sterotex (a powdered vegtable stearine produced byCapital City Products, Co., Columbus, Ohio), or other binders well knownin the art.

Advantageously, a crystalline material formed according to thisinvention is formed or combined with from about 0.05 to about 50 wt % ofat least one compound of a metallo element selected from the groupconsisting of Groups IA, IIA, IIB, and IIIB of the Periodic Table basedon the weight of crystalline material. The Periodic Table is the wellknown arrangement of chemical elements based on the periodic law and isfound in Webster's Ninth New Collegiate Dictionary, Merriam-WebsterInc., Springfield, Mass., U.S.A., (1984) at page 874.

Suitable alkali metal (Group IA), alkaline earth metal (Group IIA), lowmelting metal (Group IIB) and heavy metal (Group IIIB) compoundsincluding rare earth compounds of elements in the lanthanide series andactinide series include the oxides, hydroxides and salts of lithium,sodium, potassium, rubidium, cesium, magnesium, calcium, strontium,barium, zinc, cadmium, lanthanum, cerium, and thorium, such as lithiumhydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide,potassium oxide, sodium oxide, potassium carbonate, sodium carbonate,sodium bicarbonate, potassium nitrate, potassium borate, sodium borate,potassium chloride, potassium acetate, sodium propionate, potassiummaleate, etc. Of these, potassium, in the form of the oxide or in a formreadily convertible to the oxide, is preferred. The solid materialsformed according to this invention can be treated with from about 0.05to 50 wt % dopant based on the weight of the solid material. The alkalimetal or alkaline earth metal compound can be dry-blended with thealuminum borate, dissolved in a suitable solvent, preferably water,mixed with the solid material and dried; or aqueous solutions of samecan be added to feedstocks going to a reactor containing the solidmaterial catalyst.

Catalyst compositions of this invention are useful generally in thechemical conversion of organic compounds, particularly hydrocarbon andoxygenated hydrocarbon. In particular, chemical conversion reactionssuch as hydrogenation, dehydrogenation, isomerization, oligomerizationand oxidation have been carried out. Crystalline materials of thisinvention have been used for hydrogenation of methylbenzoate tobenzaldehyde, for dehydrogenation of methylcyclohexane to toluene, fordehydrogenation to functionalize alkylaromatic compounds ethylbenzene tostyrene, cumene to alpha-methylstyrene, and p-ethyltoluene top-methylstryene, for oligomerization of ethylene to linear butenes andpropylene to hexenes, for isomerization of o-xylene and for oxidationand/or partial oxidation of p-xylene to oxygenated aromatic products.

Particularly useful is the fact that when these solid catalystcompositions are used in liquid and/or gas phase processes, the productsof chemical conversion are easily separated from the solid catalystmaterial. Also useful is the fact that when these solid catalystcompositions are used in such fluid-phase processes, the active metalloelement components are only slowly extracted, leading to longer catalystlifetime.

Generally a process of the present invention for chemical conversioncomprising contacting under suitable reaction conditions an organicreactant in a fluid phase, i.e. liquid and/or vapor phase, with aheterogeneous catalyst composition comprising a crystalline materialhaving a chemical composition:

    (x)(M.sub.m :M'.sub.n)O.(y)Al.sub.2 O.sub.3.(z)B.sub.2 O.sub.3

where M and M' are metallo elements selected from the group consistingof nickel and cobalt, m and n are numbers from 0 to 1, inclusive, suchthat m+n=1, and x, y and z are numbers representing molar amounts of theoxides and containing a crystalline metalloaluminum borate having anX-ray diffraction pattern comprising significant lines substantially asdescribed in at least one of the tables I-IV, inclusive.

The following examples will serve to illustrate certain specificembodiments of the herein disclosed invention. These examples shouldnot, however, be construed as limiting the scope of the novel invention,as there are many variations which may be made thereon without departingfrom the spirit of the disclosed invention, as those of skill in the artwill recognize.

For example, a process for oxidation in the presence of theabove-described catalyst compositions is effected by contact of theorganic compound either in the liquid or vapor phase at temperaturesranging from about 50° C. to about 1000° C. Generally, anoxygen-containing gas is used as the oxidant. Air can be used orsynthetic mixture of an inert gas and oxygen made so as to adjust theoxygen level to the desired amount. The reaction takes place atatmospheric pressure, but the pressure may be within the range of about0 to 2000 psig. Reaction is suitably accomplished using a weight hourlyspace velocity between about 0.01 and about 100 hr⁻¹. For somecompounds, reaction in the liquid phase is preferred. Reactions in theliquid phase typically are carried out at about 50° C. to about 400° C.,preferably at about 75° C. to about 360° C. and most preferably at about100° C. to about 250° C., with pressures of about 0 to about 500 psig,preferably about 40 to about 350 psig at space velocities from about0.02 to about 5 hr⁻¹, preferably about 0.08 to about 2 hr⁻¹. Liquidphase reactions can be carried out in a trickle bed configuration,catalytic distillation configuration or slurry bed configuration, forexample. Gas phase reactions typically are carried out at about 200° C.to about 1000° C., preferably about 300° C. to about 600° C. and mostpreferably at about 400° C. to about 500° C., with pressures of about 0to about 300 psig and space velocities of about 0.01 to about 100 hr⁻¹,preferably about 0.5 to about 50 hu⁻¹. Gas phase reactions can becarried out in a fluid bed, stirred bed, fixed bed or other suitablereactor configuration.

In the context of the present invention, "partial oxidation" meanseither oxidation of less than all of the oxidizable groups on an organicreactant or the oxidation of up to all of the oxidizable groups but notcompletely to the carboxylic acid derivative.

A suitable feed for use in the oxidation and/or partial oxidationprocesses of this invention comprises an aromatic reactant having atleast one phenyl ring or a condensed aromatic ring system andsubstituted with at least one oxidizable substituent selected from thegroup consisting of alkyl, hydroxyalkyl, aldehyde, ketone groups andmixtures thereof. Each such alkyl group or the alkyl moiety of eachhydroxyalkyl group contains from 1 to 3 carbon atoms and preferablycontains one carbon atom. Preferably each oxidizable substituent is amethyl group. Thus, such typical aromatic reactants include toluene, o-,m-, or p-xylene, pseudocumene, durene, ethylbenzene, o-, m-,p-diethylbenzene, 1,2,4-triethylbenzene, 1,2,4,5-tetraethylbenzene, apropylbenzene, o-, m-, or p-dipropylbenzene, 1,2,4-triproplybenzene,1,2,4,5-tetrapropylbenzene, a methyl-, ethyl- or propylnaphthalene, adi-(methyl-, or ethyl-, or proply-) naphthalene, 4,4'-dimethylbiphenyl,4,4'-dimethyldiphenyl ether or sulfone, 3,3',4,4'-tetramenthybiphenyl,3,3',4,4'-dimethyldiphenyl ether or sulfone, or3,3',4,4'-tetramethyldiphenylpropane. Preferably the aromatic reactantis p-xylene, m-xylene, pseudocumene, durene, a dimethylnaphthalene, adi-isopropylnaphthalene, or 4,4'-dimethyldiphenyl ether or sulfone,3,3',4,4'-tetramethyldiphenyl ether or sulfone, or3,3',4,4'-tetramethyldiphenyl propane.

Although the feed can comprise a solvent, such as chlorobenzene, for thearomatic reactant, preferably a solvent is not employed. The aromaticfeed comprises preferably at least 80 weight percent, more preferably atleast 90 weight percent of the feed, in order to avoid any extensivepurification of the oxidation products. Preferably the feed consistsessentially of the aromatic reactant.

Nickel aluminum borate prepared according to the procedures outlinedabove is an active catalyst for dehydrogenation/hydrogenation reactionsin which a suitable hydrocarbon is converted to styrene,alpha-methylstyrene, or benzaldehyde.

Cobalt aluminum borate prepared according to the procedures outlinedabove is an active catalyst for reactions in which a suitablehydrocarbon is converted to benzaldehyde.

Cobalt and/or nickel aluminum borates prepared according to theprocedures outlined above are active catalysts for oxidation reactionsin which a suitable hydrocarbon is converted to a partially oxidizedproduct and/or to the carboxylic acid derivative.

Cobalt/nickel aluminum borate prepared according to the proceduresoutlined above is an active catalyst for dehydrogenation/hydrogenationreactions in which a suitable hydrocarbon is converted to styrene,alpha-methylstyrene, or benzaldehyde.

A process for the hydrogenation of methylbenzoate comprises contactinghydrogen and methylbenzoate in the vapor state with a solid materialcontaining cobalt and/or nickel, aluminum, boron and oxygen according tothis invention. Suitable conditions for the hydrogenation ofmethylbenzoate comprise a pressure of about 0.5 atmospheres to about 100atmospheres, preferably about 1 atmospheres to about 20 atmospheres, atemperature upward from the vaporization temperature of the feedstreamat operating conditions to about 600° C., preferably about 200° C. toabout 500° C., most preferably about 300° C. to 400° C., and a weighthourly space velocity (WHSV) of about 0.01 to about 100 hr⁻¹, preferablyabout 0.1 to about 10 hr⁻¹.

A process for the dehydrogenation of ethylbenzene comprises contacting afeedstream containing ethylbenzene in the vapor state with a solidmaterial containing cobalt and/or nickel, aluminum, boron and oxygenaccording to this invention. Suitable conditions for the dehydrogenationof ethylbenzene comprise a pressure of about 0.5 atmospheres to about100 atmospheres, preferably about 1 atmospheres to about 20 atmospheres,a temperature upward from the vaporization temperature of the feedstreamat operating conditions to about 900° C., preferably about 500° C. toabout 700° C., most preferably about 550° C. to 650° C., and a liquidhourly space velocity (LHSV) of about 0.01 to about 100 hr⁻¹, preferablyabout 0.1 to about 10 hr⁻¹. Advantageously, the feedstream also containsa diluent such as steam or an inert gas. The weight ratio of diluent tohydrocarbon may be any suitable value, preferably in a range from about0.1 to about 10, most preferably about 0.5 to about 5.

A process for the oligomerization of olefinic hydrocarbons comprisescontacting a feedstream containing a light olefin such as ethyleneand/or propylene in the vapor state with a solid material containingcobalt and/or nickel, aluminum, boron and oxygen according to thisinvention. Suitable conditions for the oligomerization of olefinichydrocarbons comprise a pressure of about 0.5 atmospheres to about 100atmospheres, preferably about 1 atmospheres to about 20 atmospheres, atemperature upward from the vaporization temperature of the feedstreamat operating conditions to about 800° C., preferably about 100° C. toabout 600° C., most preferably about 200° C. to 400° C., and a weighthourly space velocity (WHSV) of about 0.1 to about 20 hr⁻¹, preferablyabout 0.5 to about 5 hr⁻¹. The feedstream may also contain inertdiluents such as paraffinic hydrocarbons and/or nitrogen or other inertgas.

EXAMPLE 1

A crystalline inorganic material was prepared containing nickel,aluminum, boron and oxygen in accordance with this invention by aprocess including five steps: 1) combining ingredients in a liquidmedium, 2) gelling the combined ingredients, 3) removing substantiallyall the liquid to obtain a dry solid, 4) calcining the dry solid, and 5)washing the calcined solid.

The ingredients placed into a Waring blender were 72.7 g Ni(NO₃)₂ -6H₂ O(0.250 mol) dissolved in 75 mL warm distilled water, 193.7 q of aluminasol (7.9% alumina, 0.150 mol) and 74.2 g H₃ BO₃ (1.20 mol) dissolved in375 mL warm distilled water. These ingredients were blended for 2minutes. The resulting mixture had a pH of about 3.5-4.0. Ammoniumhydroxide, 54 mL, was added and the material was blended for fourminutes. The mint green gel had a final pH of 7.0-7.2. The gel wasplaced evenly on a 35 cm×45 cm plastic tray and allowed to air dry. Aportion, 155.47 g, of the material was placed in a vacuum oven at 120degrees C., 0.3 atm pressure with a nitrogen purge and dried to a finalweight of 111.0 g. A portion of this solid, 102.3 g, was calcinedaccording to the following program: ##STR1##

This resulted in 60.81 g of calcined material. Part of the mass (59.1 g)was placed in a 2 L round bottom flask containing 1450 mL distilledwater, and the mixture was refluxed for 6 hours. The gray solid wasremoved by filtration and dried at 120 degrees C., 0.3 atm pressure witha nitrogen purge for 6 hours. The resulting solid weighted 33.6 g. Thisproduct was analyzed by powder XRD, ICP elemental analysis and BETsurface analysis. Elemental analysis showed 33.2% nickel, 17.8%aluminum, and 6.4% boron which indicates that the crystalline materialhas the chemical composition NiAlBO₄. The BET surface area wasdetermined to be 38 m² /g and the pore volume was 0.16 cc/g. The powderXRD pattern is set out below:

    ______________________________________                                        XRD Lines for NiAlBO.sub.4                                                    Interplanar                                                                   Spacing.sup.1 Assigned                                                        d, A°  Strength.sup.2                                                                         Relative Intensity                                     ______________________________________                                        6.41 ± 0.2 W        20                                                     4.46 ± 0.1 VW        4                                                     4.09 ± 0.08                                                                              M        41                                                     4.02 ± 0.08                                                                              VW       11                                                     2.90 ±  0.05                                                                             M        29                                                     2.53 ± 0.05                                                                              M        46                                                     2.50 ± 0.05                                                                              VS       100                                                    2.42 ± 0.04                                                                              VW        8                                                     2.40 ± 0.04                                                                              VW        9                                                     2.09 ± 0.03                                                                              VW        7                                                     2.06 ± 0.03                                                                              VW        8                                                     2.04 ± 0.03                                                                              VW        9                                                     1.92 ± 0.03                                                                              W        19                                                     1.80 ± 0.03                                                                              VW       11                                                     1.74 ±  0.02                                                                             W        20                                                     1.55 ± 0.02                                                                              W        22                                                     1.50 ± 0.02                                                                              W        16                                                     1.46 ± 0.02                                                                              W        19                                                     1.35 ± 0.02                                                                              VW       11                                                     ______________________________________                                         .sup.1 Angstroms                                                              .sup.2 VW = very weak; W = weak; M = medium; S =  strong; VS = very stron                                                                              

EXAMPLE 2

Example 1 was repeated except the amount of each ingredient wasincreased by a factor of four using a larger blender. The BET surfacearea of this material was determined to be 46 m² /g.

EXAMPLE 3

Example 1 was repeated except the time of washing the calcined solidreduced to 3 hours. This product was analyzed by powder XRD and ICPelemental analysis. The XRD pattern was essentially the same as thepattern of Example 1. Elemental analysis showed 35.0% nickel, 17.1%aluminum, and 7.2% boron.

EXAMPLE 4

Example 1 was repeated except washing of the calcined solid for 2 hoursin 6M nitric acid at 60° C. This product was analyzed by powder XRD. TheXRD pattern was essentially the same as the pattern of Example 1.

EXAMPLE 5

The ingredients placed into a Waring blender were 290.8 g Ni(NO₃)₂ -6H₂O (1 mol) dissolved in 300 mL warm distilled water, 774.7 g of aluminasol (7.9% alumina, 0.6 mol) and 296.8 g H₃ BO₃ (4.8 mol) dissolved in1500 mL warm distilled water. These ingredients were blended for 2minutes. The resulting mixture had a pH of about 3.5-4.0. A total of 400mL of ammonium hydroxide was added and the material was blended. Themint green gel had a final pH of 9.0. The gel was placed evenly on atray and allowed to air dry. A portion, 542.1 g, of the material wasplaced in a vacuum oven at 120° C., 0.3 atm pressure with a nitrogenpurge and dried to a final weight of 451.9 g. A portion of this solid,113.7 g, was calcined according to the following program: ##STR2##

This resulted in 66.9 g of calcined material. Part of the mass (66.8 g)was placed in a 2 L round bottom flask containing 1500 mL distilledwater, and the mixture was refluxed for 6 hours. The gray solid wasremoved by filtration and dried at 120° C., 0.3 atm pressure with anitrogen purge for 18 hours. The resulting solid weights 38.6 g. Thisproduct was analyzed by powder XRD, ICP elemental analysis and BETsurface analysis. The XRD pattern was similar to the pattern ofExample 1. Elemental analysis showed 33.3% nickel, 18.3% aluminum, and6.9% boron. The BET surface area was determined to be 46 m² /g and thepore volume was 0.19 cc/g. This material was treated with Th(NO₃)₄ usingthe incipient wetness technique. A portion of the solid material, 5 g,and 0.595 g of Th(NO₃)₄ dissolved in minimal distilled water were placedin a crucible. The crucible was placed in a microwave oven and the wetsolid was irradiated until dryness. The dry solid was then calcined to400° C. for 6 hours to remove the nitrates.

The doped material contained 5% ThO₂ and was labeled Example 5.

EXAMPLE 6

A crystalline inorganic material was prepared containing nickel,aluminum, boron and oxygen in accordance with this invention by aprocess including five steps: 1) combining ingredients in a liquidmedium, 2) gelling the combined ingredients, 3) removing substantiallyall the liquid to obtain a dry solid, 4) calcining the dry solid, and 5)washing the calcined solid.

The ingredients placed into a Waring blender were 116.3 g Ni(NO3)2-6H20(0.400 mol) dissolved in 120 mL warm distilled water, 129.1 g of aluminasol (7.9% alumina, 0.100 mol) and 61.8 g H₃ BO₃ (1.00 mol) dissolved in300 mL warm distilled water. The contents of the blender were mixed for2 minutes. The resulting mixture had a pH of about 3.5-4.0. Ammoniumhydroxide, 45 mL, was added and the material was mixed for four minutes.The mint green gel had a final pH of 6.4. The gel was placed evenly on a35 cm×45 cm plastic tray and allowed to air dry. A portion, 180.37 g, ofthe material was placed in a vacuum oven at 120° C., 0.3 atm pressurewith a nitrogen purge and was dried to a final weight of 121.6 g. Aportion of this solid, 113.7 g, was calcined according to the followingprogram: ##STR3##

This resulted in 59.29 g of calcined material. The entire mass wasplaced in a 2 L round bottom flask containing 1450 mL distilled water,and the mixture was refluxed for 6 hours. The gray solid was removed byfiltration and dried at 120° C., 0.3 atm pressure with a nitrogen purgefor 6 hours. The resulting solid weighed 30.5 g. This product wasanalyzed by powder XRD, ICP elemental analysis and BET surface analysis.Elemental analysis showed 47.3% nickel, 11.2% aluminum, and 5.2% boronwhich indicates that the crystalline material has the chemicalcomposition Ni₂ AlBO₅. The BET surface area was determined to be 63 m²/g and the pore volume 0.295 cc/g. The powder XRD pattern is set outbelow:

    ______________________________________                                        XRD Lines for Ni.sub.2 AlBO.sub.5                                             Interplanar                                                                   Spacing.sup.1 Assigned                                                        d, A°  Strength.sup.2                                                                         Relative Intensity                                     ______________________________________                                        5.01 ± 0.2 M        42                                                     4.55 ± 0.10                                                                              M        50                                                     3.66 ± 0.08                                                                              W        21                                                     2.72 ± 0.05                                                                              W        17                                                     2.64 ± 0.05                                                                              W        15                                                     2.51 ±  0.04                                                                             S        95                                                     2.47 ± 0.04                                                                              VS       100                                                    2.29 ±  0.03                                                                             M        28                                                     2.28 ± 0.03                                                                              W        19                                                     2.27 ± 0.03                                                                              W        14                                                     2.12 ± 0.03                                                                              W        22                                                     2.10 ± 0.03                                                                              W        17                                                     2.08 ± 0.03                                                                              W        23                                                     1.99 ± 0.03                                                                              M        32                                                     1.87 ± 0.03                                                                              M        40                                                     1.72 ± 0.03                                                                              VW       10                                                     1.54 ± 0.02                                                                              W        22                                                     1.47 ± 0.02                                                                              W        22                                                     1.46 ± 0.02                                                                              M        31                                                     1.44 ± 0.02                                                                              W        19                                                     ______________________________________                                         .sup.1 Angstroms                                                              .sup.2 VW = very weak; W = weak; M = medium; S = strong; VS = very strong

EXAMPLE 7

The preparation of Example 6 was repeated with the dry solid beingcalcined to a temperature of 1020° C. for 8 hours. This product wasanalyzed by powder XRD, ICP elemental analysis and BET surface analysis.Elemental analysis showed 48% nickel, 10.5% aluminum, and 4.4% boron.The BET surface area was determined to be 5 m² /g.

COMPARATIVE EXAMPLE A

The ingredients placed into a Waring blender were 16.6 g Ni(NO₃)₂ -6H₂ 0(0.0571 mol) dissolved in 20 mL warm distilled water, 567.7 g of aluminasol (7.6% alumina, 0.428 mol) and 10.6 g H₃ BO₃ (0.172 mol) dissolved in50 mL warm distilled water. The contents of the blender were mixed for 2minutes. After mixing the mixture had a pH of 5.0. Ammonium hydroxide,5.6 mL, was added with mixing to the blender and the mixture was blendedfor 4 minutes. The mint green gel had a final pH of 5.5. The gel wasplaced evenly on a 35 cm×45 cm plastic tray and allowed to air dry. Aportion, 87.92 g, of the material was placed in a vacuum oven at 120°C., 0.3 atm pressure with a nitrogen purge and dried to a final weightof 76.51 g. A portion of this solid, 58.98 g, was calcined according tothe following program: ##STR4##

This resulted in 38.0 g of calcined material.

COMPARATIVE EXAMPLE B

The ingredients placed into a Waring blender were 29.1 g Ni(NO₃)₂dissolved in 30 mL warm distilled water and 134.2 q of alumina sol (7.6%alumina, 0.100 mol) with 100 mL distilled water. The contents of theblender were mixed 6 minutes. After blending the mixture had a pH of5.0. The mint green gel was placed evenly on a 35 cm×45 cm plastic trayand allowed to air dry. A portion, 24.18 g, of the material was placedin a vacuum oven at 120° C., 0.3 atm pressure with a nitrogen purge anddried to a final weight of 19.26 g. A portion of this solid, 5.50 g, wascalcined according to the following program: ##STR5##

This resulted in 2.88 g of calcined material. The material wasidentified by its XRD pattern which matched that of nickel aluminate.

COMPARATIVE EXAMPLE C

The ingredients placed into a mortar were 29.1 g

Ni(NO₃ )₂ -6H₂ O (0.100 mol) and 4.1 g H₃ BO₃ (0.067 mol) and groundtogether with a pestle as quickly as possible because the mixture ishygroscopic. A portion, 7.17 g, of the ground material was placed in acalcination oven and

calcined according to the following program: ##STR6##

The 2.00 g of calcined material was identified by its XRD pattern whichmatched that of nickel borate.

EXAMPLES 8-12 AND COMPARATIVE EXAMPLES D-F

In these examples the catalysts prepared in Examples 1, 2, 3, 5 and 6and Comparative Examples A, B and C were tested as catalysts forconversion of methylbenzoate (PhCOOMe), to benzaldehyde (PhCHO), inExamples 8, 9, 10, 11 and 12 and Comparative Examples D, E and Frespectively.

For screening, the catalyst was ground and sieved to 18/35 mesh and 5.00g was placed on a quartz frit in a 19 mm OD quartz reactor tube. A 5 mmOD quartz thermowell was fitted axially in the catalyst bed. The reactortube was placed in an electrically heated tube furnace with the catalystbed centered in the heated zone and heated to the desired reactiontemperature under nitrogen flow. The gas supply was then switched tohydrogen and the flow of liquid reactant was begun. The hydrogen flowrate was set to 30 mL/min using a Brooks mass flow controller. Themethylbenzoate was introduced through a stainless steel tube which endedagainst the thermowell, allowing the liquid to flow down the thermowelland vaporize above the catalyst bed. Generally, the liquid flow rate wasset to 0.0148 mL/min with a syringe pump. Assuming a catalyst density of1 g/mL, this gives a space velocity WHSV=0.18 and a contact time of 5sec at 350° C. The conversion and selectivity reported for hydrogenationof methylbenzoate over catalysts containing nickel for Examples 9-11were obtained at WHSV of 0.05 to 0.06 hr⁻¹. At calculated WHSV of 0.119hr⁻¹ a conversion of 30% and a selectivity of 60% were obtained inExample 9. At calculated WHSV of 0.117 hr⁻¹ a conversion of 6.5% and aselectivity of 21% were obtained in Example 10. At calculated WHSV of0.115 hr⁻¹ a conversion of 25.5% and a selectivity of 24% were obtainedin Example 11.

Products from runs of about 2 hrs duration were collected in a dry icecooled trap at the outlet of the reactor. The liquid collected wasanalyzed by GC using a Superox capillary column. The conversion andselectivity data given below was based on uncorrected FID area percentsof methylbenzoate and benzaldehyde. Methanol was also detected in allcases, but it was not used in quantization because of the detector'srelative insensitivity to it. Other by-products were benzene, toluene,small amounts of several unidentified heavies, and occasionally benzylalcohol. Only benzene and toluene were present in large amounts.

    ______________________________________                                        Hydrogenation of Methyl Benzoate                                              over Catalysts Containing Nickel                                                                          PhCOOMe  PhCHO                                    Example Catalyst   Temp     conversion                                                                             selectivity                              ______________________________________                                         8      NiAlBO.sub.4                                                                             350° C.                                                                         6.4%      73%                                             Example 1  375      12.3     70                                                          400      24.8     70                                        9      NiAlBO.sub.4                                                                             350      69.0     78                                               Example 2                                                             10      NiAlBO.sub.4                                                                             350      20.0     58                                               Example 3                                                                     Nitric acid                                                                   Leached                                                               11      NiAlBO.sub.4                                                                             350      32.0     22                                               Example 5                                                                     Th                                                                    12      Ni.sub.2 AlBO.sub.5                                                                      350      4.8      49                                               Example 6  375      9.4      54                                                          400      21.6     40                                       D       Amorphous  350      2.5      24                                               Example A  375      7.3      26                                                          400      24.1     19                                       E       NiAl.sub.2 O.sub.4                                                                       350      26.8     16                                               Example B  400      78.2     36                                       F       Ni.sub.3 (BO.sub.2).sub.2                                                                350      2.4       0                                               Example C  400      5.2       3                                       ______________________________________                                    

After use in Example 12 the catalyst prepared as in Example 6 was againanalyzed. Comparative data for surface analysis, given below, indicateno substantial change in the character of the catalyst during use.

    ______________________________________                                        Surface Analysis of Catalyst Before and After                                 Use in Hydrogenation of Methyl Benzoate                                       Analysis in Atom Percent                                                      Element       Before Use                                                                              After Use                                             ______________________________________                                        Carbon        20.3      16.1                                                  Oxygen        42.7      44.4                                                  Aluminum      13.5      14.8                                                  Boron         10.6      12.6                                                  Nickel        11.7      11.9                                                  ______________________________________                                    

EXAMPLE 13

In this example, inorganic solid material prepared as in Example 6 wastested as a catalyst for dehydrogenation of ethylbenzene to styrene.

The solid material described above was ground and sieved to 12-24 mesh.A 24.7 g, 41.0 cc sample was placed into a low-nickel, stainless steeltubular reactor which was operated isothermally at 1100° F. Ethylbenzeneand steam were fed though the reactor simultaneously. Downstream fromthe reactor a condenser and gas-liquid-separator collected productsamples during a 24-hour period. The results are summarized as below:

Temperature 587° C. (1100° F.)

LHSV=1.0/hr

Steam to hydrocarbon (wt. to wt.)=2.0

Conversion 22.4%

Selectivity 73%

Benzene/toluene ratio=2:1

Yield=16%

EXAMPLE 14

A crystalline inorganic material was prepared containing cobalt,aluminum, boron and oxygen in accordance with this invention by aprocess including five steps: 1) combining ingredients in a liquidmedium, 2) gelling the combined ingredients, 3) removing substantiallyall the liquid to obtain a dry solid, 4) calcining the dry solid, and 5)washing the calcined solid.

The ingredients placed into a Waring blender were 203.7 g Co(NO₃)₂₋ 6H₂O (0.700 mol) dissolved in 200 mL 198.7 g of PHF alumina sol (7.7% AL₂O₃ by wt., 0.150 mol) and 18.5 g H₃ BO₃ (0 300 mol) dissolved in 90 mLof warm distilled water. The contents of the blender were mixed oneminute on low and on minute on high speed. The resulting deep raspberrycolored thick gel had a pH of 3.5. Addition of 5.2 mL of NH₄ OH andsubsequent blending for one minute resulted in a thinner grape-raspberrycolored gel which had a pH of 4.5-5.0. Continued blending for sixminutes, and air drying on a 35 cm×45 cm tray resulted in 192.9 g ofmaterial. Drying this material in a vacuum oven for 21 hrs at 0.3 atmand 120° C. resulted in 81.4 g of large dark purple chunks. Part of thispurple solid, 9.35 g, was calcined in air using the following program:##STR7##

This product was analyzed by powder XRD, ICP elemental analysis and BETsurface analysis. Elemental analysis showed 50.0% cobalt, 9.5% aluminum,and 4.6% boron which indicates that the crystalline material has thechemical composition Co₂ AlBO₅. The BET surface area was determined tobe 6 m² /g, with a pore volume of 0.018 cc/g. The powder XRD pattern isset out below:

    ______________________________________                                        XRD Lines for Co.sub.2 Al B O.sub.5                                           Interplanar                                                                   Spacing.sup.1 Assigned                                                        d, A°  Strength.sup.2                                                                         Relative Intensity                                     ______________________________________                                        5.03 ± 0.2 M        54                                                     4.60 ± 0.1 M        36                                                     3.68 ± 0.08                                                                              W        18                                                     2.78 ± 0.05                                                                              VW       10                                                     2.68 ± 0.05                                                                              VW       10                                                     2.52 ± 0.04                                                                              VS       100                                                    2.32 ± 0.04                                                                              W        23                                                     2.30 ± 0.04                                                                              W        15                                                     2.13 ± 0.04                                                                              W        18                                                     2.12 ± 0.04                                                                              W        13                                                     2.11 ± 0.04                                                                              W        18                                                     2.02 ± 0.03                                                                              W        20                                                     1.89 ± 0.03                                                                              M        28                                                     1.83 ± 0.02                                                                              VW        8                                                     1.75 ± 0.02                                                                              VW        8                                                     1.69 ± 0.02                                                                              VW        5                                                     1.56 ± 0.02                                                                              W        18                                                     1.50 ± 0.02                                                                              W        15                                                     1.47 ± 0.02                                                                              W        15                                                     1.46 ± 0.02                                                                              W        13                                                     1.43 ± 0.02                                                                              VW        8                                                     1.37 ± 0.02                                                                              W        13                                                     ______________________________________                                         .sup.1 Angstroms                                                              .sup.2 VW = very weak; W = weak; M = medium; S = strong; VS = very strong

Material prepared as in this Example was tested as a catalyst for thehydrogenation of methylbenzoate to benzaldehyde as described above. Thematerial gave a conversion of 6% and a selectivity to benzaldehyde of51%.

The oxidation capability of material prepared as in this Example wastested by running atmospheric oxidations of p-xylene with air at atemperature of 120° C. in a glass reactor equipped with a glass frit forsupporting the solid catalyst and dispersing the air. Solid catalyst,1.12 g, and p-xylene, 80 mL, were placed in the glass reactor. Air flowwas controlled at 100 mL/min during a 6-hour reaction period. Oxidationactivity was observed with an oxygen monitor, calibrated with air toread 20.9%. The monitor reading doped to 20.5% oxygen during theoxidation. The liquid product was a very pale yellow and contained only0.05 ppm dissolved cobalt.

EXAMPLES 15-17

These examples describe the preparation of solid solutions containingnickel, cobalt, aluminum, boron, and oxygen prepared according to thisinvention.

Solutions of nickel nitrate hexahydrate (105.9 g dissolved in 110 mL ofwarm deionized water), cobalt nitrate hexahydrate (10.59 dissolved in 20mL warm deionized water) and boric acid (61.8 g in 300 mL warm deionizedwater) were added to 110.0 g of Al₂ O₃ PHF alumina sol in a Waringblender. The mixture was blended for 3 minutes, yielding a mixture witha pH of 3.5. Addition of 45 mL of ammonium hydroxide, with subsequentblending at low speed, yielded a material with a pH of 6.4. The thin,gel-like material was poured out onto a plastic tray and allowed to airdry. The air dried sample, 151.5 g, was vacuum dried at 120° C. and 0.3atm for 15 hrs with a nitrogen purge. The resulting product had a weightof 124.3 g. This sample was calcined and labeled Example 15.

Solutions of nickel nitrate hexahydrate (87.2 g, 0.30 mol, in 90 mL warmdeionized water), cobalt nitrate hexahydrate (29.1 g, 0.10 mol, in 30 mLwarm deionized water), and boric acid (61.8 g, 1.00 mol, in 300 mL warmdeionized water) were added to a Waring blender with 119.2 g of an 8.56%Al₂ O₃ PHF alumina sol (0.10 mol Al₂ O₃). The material was blended for 3minutes on low speed, stirred, and blended on low speed for anadditional 30 seconds. The mixture had a pH of approximately 4. Additionof 47 mL of ammonium hydroxide raised the pH to about 6.4. The thingel-like material was poured out onto a 35 cm×45 cm plastic tray andallowed to air dry. The air dried material, 165.5 g, was vacuum dried at120° C. and 0.3 atm. for 60 hrs with a nitrogen purge. The yield was124.9 g.

A 26.52 g portion was calcined in air for two weeks at 830 C, yielding14.54 g. of calcined solids. The sample was removed from the oven andground with a mortar and pestle. A portion of the ground solids, 11.69g, was recalcined at 830 C for an additional 15 days. The final weightwas 11.3 g. This sample was calcined and labeled Example 16.

Solutions of nickel nitrate hexahydrate (58.2 g, 0.20 mol, dissolved in60 mL of warm deionized water), cobalt nitrate hexahydrate (58.2 g, 0.20mol, dissolved in 60 mL of warm deionized water), and boric acid (61.8g, 1.00 mol, in 300 mL of warm deionized water) were added in 119.2 g ofan 8.56% Al₂ O₃ PHF alumina sol (0.10 mol A₂ O₃) into a Waring blender.The mixture was blended for 3 minutes. Addition of 46 mL of ammoniumhydroxide, with subsequent blending at low speed, yielded a mixture witha pH of 6.2. The thin, gel-like material was poured out onto a 35 cm×45cm plastic tray and allowed to air dry. The air dried sample, 166.6 g,was vacuum dried at 120° C. and 0.3 atm with a nitrogen purge for 60hrs. The resultant product had a weight of 115.6 g. A 27.55 g sample wascalcined as above, yielding 15.9 g of product. A 7.74 g sample,recalcined as above after grinding, yielded 7.45 g. This sample wascalcined and labeled Example 17.

The principal lines of the XRD patterns for the five samples prepared asin Examples 6, 15-17, and 14 are set out below:

    ______________________________________                                        Principal XRD Lines for Solid Solutions                                       Example no.                                                                   6       15        16         17      14                                       Ni/Co                                                                         1.0/0.0 0.9/0.1   0.75/0.25  0.5/0.5 0.0/1.0                                  d/RI.sup.1                                                                    ______________________________________                                        5.01/42 5.01/42   5.02/46    4.98/41 5.03/54                                  4.55/50 4.56/52   4.56/51    4.54/41 4.60/36                                  3.66/21 3.66/18   3.67/22    3.65/22 3.68/18                                  2.51/95 2.51/76   2.51/91    2.50/100                                                                              2.52/49                                  2.47/100                                                                              2.47/100  2.48/100   2.48/80 2.51/100                                 2.29/28 2.29/26   2.30/28    2.30/28 2.32/23                                  1.99/32 1.99/26   2 00/27    2.00/29 2.02/20                                  1.87/40 1.87/24   1.87/31    1.87/34 1.89/28                                  ______________________________________                                         .sup.1 Interplanar Spacing, Angstroms/Relative Intensity                 

Five samples prepared as in Example 6, 15-17, and 14 were analyzed forunit cell parameters, a, b, and c, and cell volumes, V, calculated asthe product a.b.c. The cell volumes change smoothly with mole fractionof the metal oxide phase. The data appear below:

    ______________________________________                                        Orthorhombic Cell Dimensions                                                  in (Co:Ni).sub.2 Al(BO.sub.3)O.sub.2 Phases                                   Preparation                                                                            a, A      b, A       c, A    V, A.sup.3                              ______________________________________                                        Ni       9.0934(29)                                                                              12.0035(32)                                                                              2.9411(7)                                                                             321.0                                   Ni.sub.0.9 :Co.sub.0.1                                                                 9.0828(20)                                                                              12.0124(44)                                                                              2.9451(7)                                                                             322.1                                   Ni.sub.0.75 :Co.sub.0.25                                                               9.1443(15)                                                                              12.0090(39)                                                                              2.9509(8)                                                                             324.1                                   Ni.sub.0.5 :Co.sub.0.5                                                                 9.1685(49)                                                                              11.9996(125)                                                                             2.9586(26)                                                                            325.4                                   Co       9.2041(6) 12.0376(8) 2.9997(3)                                                                             332.4                                   ______________________________________                                         .sup.1 Angstroms                                                         

The ingredients placed into a Waring blender were 0.36 g zinc nitratehydrate (0.00125 mol), 72.3 g Ni(NO₃)₂ -6H₂ O (0.249 mol) dissolved in70 mL warm deionized water, 178.7 g of alumina sol (8.6% alumina, 0.150mol) and 74.2 g H₃ BO₃ (1.2 mol) dissolved in 370 mL warm deionizedwater. The contents of the blender were mixed for 2 minutes. Aftermixing the mixture had a pH of 3.5. Ammonium hydroxide, 75 mL, was addedwith mixing to the blender and the mixture was blended for 3 minutes.The thin gel had a final pH of 8.5. The gel was placed evenly on a 35cm×45 cm plastic tray and allowed to air dry. The dry solid, 141.4 g,was placed in a vacuum oven at 120° C., 0.3 atm pressure with a nitrogenpurge and dried for 20 hours. After drying a portion of the dry solid,45.8 g, was calcined according to the following program: ##STR8##

This resulted in 27.7 g of calcined material which had a smoky bluecolor. The large chunks of calcined material were powdered and placed ina 1-liter round bottom flask with 500 mL of deionized water and refluxedfor 3 hours. The undissolved solid was recovered by vacuum filtrationand dried for 18 hours in a vacuum oven with a nitrogen purge at atemperature of 120° C. and a pressure of 0.3 atm. This solid materialwas tested as a catalyst for hydrogenation of methylbenzoate asdescribed hereinabove. At a WHSV of 0.062 hr⁻¹ and a reactiontemperature of 350° C., the conversion of methylbenzoate was 41.5% andselectivity to benzaldehyde was 86%.

EXAMPLE 19

This example describes the preparation of a solid solution containingnickel, cobalt, aluminum, boron, and oxygen prepared according to thisinvention.

Solutions of nickel nitrate hexahydrate (185.2 g, 0.636 mol, dissolvedin 180 mL of warm deionized water), cobalt nitrate hexahydrate (18.5 g,0.0636 mol, dissolved in 20 mL of warm deionized water) and boric acid(49.5 g, 0.8 mol, in 250 mL warm deionized water) were added to 172.3 gof Al₂ O₃ PHF alumina sol in a Waring blender. The mixture was blendedfor 3 minutes at low speed, yielding a mixture with a pH of 4. Additionof 35 mL of ammonium hydroxide, with subsequent blending at low speed atlow speed, yielded a material with a pH of 6.4. This raspberry coloredgel was poured out onto a plastic tray and allowed to air dry. The airdried sample, 167.5 g, was vacuum dried at 120° C. and 0.3 atm for 18hrs with a nitrogen purge. The resulting product had a weight of 167.5g. A portion of this solid, 19.21 g, was calcined according to thefollowing program: ##STR9##

This resulted in 10.1 g of calcined material. This product was analyzedby powder XRD, ICP elemental analysis and BET surface analysis. The XRDpattern was essentially the same as the pattern of Table IV. Elementalanalysis showed 40.0% cobalt, 4.5% nickel, 10.6% aluminum, and 9.8%boron. The BET surface area was determined to be 2.2 m² /g.

What is claimed is:
 1. A crystalline material comprising aluminum,boron, oxygen and cobalt having an X-ray diffraction pattern comprisingsignificant lines substantially as described in at least one of theTables I through IV, inclusive.
 2. The crystalline material of claim 1with a binder.
 3. The crystalline material of claim 1 with from about0.05 to about 50 wt % of at least one metallo element selected from thegroup consisting of Groups IA, IIA, IIB, and IIIB of the Periodic Tablebased on the weight of crystalline material.
 4. The composition of claim1 comprising crystalline Co₂ AlBO₅ having the X-ray diffraction powderpattern comprising significant lines substantially as described in TableIII.
 5. The process of making the crystalline material of claim 1 whichcomprises dispersing in a liquid medium a source of alumina, a source ofboria, and a source of cobalt (II) ions, removing substantially all theliquid to form a superficially dry solid, and calcining thesuperficially dry solid at a temperature in a range from about 600° toabout 1500° C.
 6. The process of making the crystalline material ofclaim 4, which comprises forming an aqueous composition comprising asource of cobalt ions, a source of alumina, and a source of boria, at apH in a range from about 4 to about 9, drying the mixture to form asuperficially dry solid, and calcining the dry solid at a temperature ina range from about 700° to about 1100° C. to form a calcined solid. 7.The process of claim 6 wherein the aqueous mixture comprises aqueousammonia.